[go: up one dir, main page]

EP0331941B1 - Process for the preparation of cold-hardening flexible polyurethane foams having excellent deadening properties - Google Patents

Process for the preparation of cold-hardening flexible polyurethane foams having excellent deadening properties Download PDF

Info

Publication number
EP0331941B1
EP0331941B1 EP89102703A EP89102703A EP0331941B1 EP 0331941 B1 EP0331941 B1 EP 0331941B1 EP 89102703 A EP89102703 A EP 89102703A EP 89102703 A EP89102703 A EP 89102703A EP 0331941 B1 EP0331941 B1 EP 0331941B1
Authority
EP
European Patent Office
Prior art keywords
weight
polyether
component
polyol
und
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP89102703A
Other languages
German (de)
French (fr)
Other versions
EP0331941A1 (en
Inventor
Peter Dr. Gansen
Rudi Wolfgramm
Klaus-Dieter Dr. Wolf
John J. Lindsey
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Bayer Corp
Original Assignee
Bayer AG
Miles Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6348478&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0331941(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Bayer AG, Miles Inc filed Critical Bayer AG
Publication of EP0331941A1 publication Critical patent/EP0331941A1/en
Application granted granted Critical
Publication of EP0331941B1 publication Critical patent/EP0331941B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2350/00—Acoustic or vibration damping material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S521/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S521/914—Polyurethane cellular product formed from a polyol which has been derived from at least two 1,2 epoxides as reactants

Definitions

  • Cold-curing flexible polyurethane foams are usually used to manufacture upholstery elements.
  • the elasticity of the conventional cold foam makes it suitable for use as a seat cushion.
  • Cold-curing polyurethane foams can be produced using special, soft-molded foam atypical raw material combinations, which, in contrast to the usual cold foams, have a favorable damping behavior. These so-called "tired" foams are suitable for sound insulation purposes and for all applications that require good damping.
  • the open-cell polyurethane foams with high flow resistance meet the requirements of an acoustician for an airborne sound absorber (cf. H. Schmidt: Schalltechnisches Wörterbuch, Düsseldorf 1984).
  • the Airborne sound absorption which is caused by external friction at interfaces, is essentially determined by the cell structure and the open-cell structure of a foam. These foam properties can be set within certain limits for cold-curing flexible polyurethane foams without having to change the basic raw materials, ie polyol and isocyanate.
  • the open porosity alone is not sufficient for absorption in the lower frequency range - the structure of the flexible polyurethane foam must have intensive damping, particularly for structure-borne sound absorption.
  • the damping behavior which is characterized by the loss factor, can be significantly improved in the case of polyurethane foams, in particular by using special polyols and / or isocyanates.
  • DE-AS 2 751 774 describes, for example, a sound-absorbing composite system which contains a flexible polyurethane foam as a spring in a mass / spring system.
  • the soft foam described there has a good damping behavior, as a result of which the collapse of coincidence in a frequency range between 150 and 10,000 Hz is avoided.
  • the good damping is achieved by a combination of raw materials, which contains about 20% rigid foam polyol with a hydroxyl number of about 400 and 80% of a soft foam polyol with a hydroxyl number of about 50.
  • An additional insulation and damping effect is achieved by using heavy spar as an inorganic additive.
  • DE-OS 3 313 624 describes a raw material combination whose hydroxyl-containing component includes contains at least two different polyether polyols.
  • One of these polyols must have an OH number of 180 to 400 and be present in the polyol mixture in a concentration of at least 15% by weight. You can use it with flexible polyurethane foams. Produce elastic moduli of about 5 ⁇ 10 ⁇ N / m2 and loss factors of about 0.35.
  • the object of the present invention was to find a frame material combination which allows the production of highly damping foams; this means foams whose loss factors have at least a value of 0.5, but preferably reach loss factor values greater than 0.9.
  • a process is preferred which is characterized in that the polyisocyanate is reacted with the polyether component c) in a first stage to form a prepolymer having isocyanate groups, which is then subsequently reacted with the polyol components a) and b) in the presence of water and / or organic blowing agents, catalysts and foam stabilizers and optionally further auxiliaries and additives.
  • the polyol component b) is preferably in an amount of 10 to 20% by weight, based on the polyol components a), b) and c), and the polyether component c) in an amount of 30 to 70% by weight, based on the polyether components a), b) and c) used.
  • the polyether component c) preferably has an OH number of 25 to 100.
  • aromatic polyisocyanates are preferably used as polyisocyanates.
  • the polyether component a) preferably has an OH number of 25 to 40.
  • component b) containing OH groups is an at least trifunctional polyether with an OH number of 150 to 400 based on propylene oxide.
  • surface-active additives and foam stabilizers to be used according to the invention as well as cell regulators, reaction retarders, stabilizers, flame-retardant substances, plasticizers, dyes and fillers, as well as fungistatic and bacteriostatic substances, as well as details on the use and mode of action of these additives are given in the Plastics Manual, Volume VII by Vieweg and Höchtlen, Carl-Hanser-Verlag, Kunststoff 1966, e.g. on pages 103-113.
  • the reaction components are reacted according to the one-step process, the prepolymer process or the semi-prepolymer process, which are known per se, machine equipment often being used, for example those described in US Pat. No. 2,764,565. Details about processing devices, which are also suitable according to the invention, are found in Kunststoff-Handbuch, Volume VII, edited by Vieweg and Höchtlen, Carl-Hanser-Verlag, Kunststoff 1966, e.g. B. on pages 121-205.
  • all components are implemented with a key figure above 70, preferably with a key figure from 70 to 115.
  • the key figure a term used very often in the production of polyurethane foams, says something about the degree of crosslinking of a foam. It is customary to consider that foam with the code number 100, in which the stoichiometric ratio or the theoretically necessary amount of isocyanate was used. With the help of the key figure it is possible to define the degree of under- or over-networking in more detail.
  • the key figure is calculated according to the general formula as follows:
  • the foaming is carried out in closed molds.
  • the reaction mixture is introduced into a mold.
  • Metal for example aluminum or plastic, for example epoxy resin, can be used as the molding material.
  • the foamable reaction mixture foams in the mold and forms the shaped body.
  • the flexible molded foams produced according to the invention are in a bulk density range of 25 to 250 kg / m 3, loss factors of over 0.8 being achieved without the addition of inorganic and / or organic fillers.
  • the polyurethane foams can be soft to hard depending on the key figure and blowing agent content, without losing their flexibility.
  • MDI 85/20 Mixture of 65% 4,4 'and 20% 2,4'-diisocyanatodiphenylmethane and 15% higher functional polyisocyanates of the diphenylmethane series.
  • reaction mixture 100 parts by weight of the A component are mixed intensively with 45.5 parts by weight of the B component (code 86).
  • the reaction mixture is introduced into a cuboid metal mold heated to 50 ° C., the mold is closed with a metal lid and the reaction mixture foams.
  • the resulting flexible polyurethane foam has the following mechanical properties: Gross density (DIN 53 420) 81 kg / m3 Tensile strength (DIN 53 571) 95 kPa Elongation at break (DIN 53 571) 140% Compression hardness 40% (DIN 53 577) 4.4 kPa Compression set (50%, 22 h, 70 ° C, DIN 53 572) 2.9% Rebound resilience (DIN 53 573) 14% Loss factor (determined according to the stroke vibration method) 0.88
  • polyol A 15 parts by weight of polyol B 60 parts by weight of polyol C 2.5 parts by weight of water 0.3 part by weight of dimethylethanolamine 0.6 parts by weight of triethylene diamine (33% by weight in dipropylene glycol) 0.83 parts by weight of bis-dimethylaminopropylamine 1.0 part by weight of triethanolamine 1.0 part by weight of silicone stabilizer B 4900 from Goldschmidt AG, Essen.
  • Mixture of 40% TDI 65 and 60% MDI raw 100 parts by weight of the A component are mixed intensively with 43.1 parts by weight of the B component (code number 90).
  • the reaction mixture is introduced into a cuboid metal mold heated to 50 ° C., the mold is closed with a metal lid and the reaction mixture foams.
  • a molded part with the following properties is produced from 100 parts by weight of component A and 41.1 parts by weight of component B (code number 90) as in Example 1: Gross density (DIN 53 420) 82 kg / m3 Compression hardness 40% (DIN 53 571) 3.9 kPa Loss factor (determined according to the lift swing method) 0.57
  • Example 4 a phase-stable formulation is possible by prepolymerizing the flexible foam polyol (polyether component a)). 40 parts by weight of a sorbitol-started polyoxypropyloxyethylene polyol with an OH number of 100 and 82.2% terminal oxyethylene groups (polyol D).
  • reaction of 80 parts by weight of MDI 85/20 with 20 parts by weight of polyol A results in a semiprepolymer with an NCO content of about 25%.
  • the reaction is carried out at room temperature with constant stirring. The reaction is complete after 24 hours.
  • a molded part with the following properties is produced from 100 parts by weight of component A and 91.5 parts by weight of component B (code number 70) as in Example 1: Gross density (DIN 53 420) 92 kg / m3 Compression hardness 40% (DIN 53 571) 5.04 kPa Loss factor (determined according to the lift swing method) 1.09
  • MDI 85/20 100 parts by weight of the A component are mixed intensively with 43.8 parts by weight of the B component (code number 80) and introduced into a metal mold as in Example 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Description

Kalthärtende Polyurethan-Weichformschaumstoffe werden üblicherweise zur Herstellung von Polsterelementen eingesetzt. Die Elastizität der konventionellen Kaltschäume macht sie für einen Einsatz als Sitzkissen geeignet. Unter Einsatz spezieller, Weichformschaum-untypischer Rohstoffkombinationen kann man kalthärtende Polyurethanschäume herstellen, die im Gegensatz zu den üblichen Kaltschäumen ein günstiges Dämpfungsverhalten aufweisen. Diese sog. "müden" Schäume sind zu Schallschutzzwecken und für alle Anwendungen, die gute Dämpfung erfordern, geeignet.Cold-curing flexible polyurethane foams are usually used to manufacture upholstery elements. The elasticity of the conventional cold foam makes it suitable for use as a seat cushion. Cold-curing polyurethane foams can be produced using special, soft-molded foam atypical raw material combinations, which, in contrast to the usual cold foams, have a favorable damping behavior. These so-called "tired" foams are suitable for sound insulation purposes and for all applications that require good damping.

Die offenzelligen Polyurethanschäume mit hohem Strömungswiderstand erfüllen die Anforderungen eines Akustikers an einen Luftschallabsorber (vgl. H. Schmidt: Schalltechnisches Wörterbuch, Düsseldorf 1984). Die Luftschallabsorption, die durch äußere Reibung an Grenzflächen entsteht, wird im wesentlichen durch die Zellstruktur und die Offenporigkeit eines Schaumes determiniert. Diese Schaumeigenschaften lassen sich bei kalthärtenden Polyurethan-Weichformschaumstoffen in gewissen Grenzen einstellen, ohne die Basisrohstoffe, d.h. Polyol und Isocyanat verändern zu müssen. Die Offenporigkeit allein reicht für eine Absorption im unteren Frequenzbereich nicht aus - insbesondere zur Körperschallabsorption muß das Gerüst des Polyurethanweichschaumes über eine intensive Dämpfung verfügen.The open-cell polyurethane foams with high flow resistance meet the requirements of an acoustician for an airborne sound absorber (cf. H. Schmidt: Schalltechnisches Wörterbuch, Düsseldorf 1984). The Airborne sound absorption, which is caused by external friction at interfaces, is essentially determined by the cell structure and the open-cell structure of a foam. These foam properties can be set within certain limits for cold-curing flexible polyurethane foams without having to change the basic raw materials, ie polyol and isocyanate. The open porosity alone is not sufficient for absorption in the lower frequency range - the structure of the flexible polyurethane foam must have intensive damping, particularly for structure-borne sound absorption.

Das Dämpfungsverhalten, welches durch den Verlustfaktor charakterisiert wird, kann bei Polyurethanschaumstoffen, insbesondere durch den Einsatz spezieller Polyole und/oder Isocyanate deutlich verbessert werden. Die DE-AS 2 751 774 beschreibt z.B. ein schalldämmendes Verbundsystem, das als Feder in einem Masse/Feder-System einen Polyurethanweichschaumstoff enthält. Der dort beschriebene Weichschaumstoff hat ein gutes Dämpfungsverhalten, wodurch der Koinzidenzeinbruch in einen Frequenzbereich zwischen 150 bis 10.000 Hz vermieden wird. Erreicht wird die gute Dämpfung durch eine Rohstoffkombination, welche etwa 20 % Hartschaumpolyol mit einer Hydroxylzahl von etwa 400 und 80 % eines Weichschaumpolyols mit einer Hydroxylzahl von etwa 50 beinhaltet. Eine zusätzliche Dämm- und Dämpfungswirkung wird durch den Einsatz von Schwerspat als anorganischem Zuschlagstoff erreicht.The damping behavior, which is characterized by the loss factor, can be significantly improved in the case of polyurethane foams, in particular by using special polyols and / or isocyanates. DE-AS 2 751 774 describes, for example, a sound-absorbing composite system which contains a flexible polyurethane foam as a spring in a mass / spring system. The soft foam described there has a good damping behavior, as a result of which the collapse of coincidence in a frequency range between 150 and 10,000 Hz is avoided. The good damping is achieved by a combination of raw materials, which contains about 20% rigid foam polyol with a hydroxyl number of about 400 and 80% of a soft foam polyol with a hydroxyl number of about 50. An additional insulation and damping effect is achieved by using heavy spar as an inorganic additive.

Die DE-OS 3 313 624 beschreibt eine Rohstoffkombination, deren hydroxylhaltige Komponente u.a. mindestens zwei verschiedene Polyetherpolyole enthält. Eines dieser Polyole muß eine OH-Zahl von 180 bis 400 haben und in einer Konzentration von mindestens 15 Gew.-% im Polyolgemisch vorliegen. Man kann damit Polyurethanweichschäume mit. Elastizitätsmodulen von etwa 5·10⁵ N/m² und Verlustfaktoren von etwa 0,35 herstellen.DE-OS 3 313 624 describes a raw material combination whose hydroxyl-containing component includes contains at least two different polyether polyols. One of these polyols must have an OH number of 180 to 400 and be present in the polyol mixture in a concentration of at least 15% by weight. You can use it with flexible polyurethane foams. Produce elastic moduli of about 5 · 10 · N / m² and loss factors of about 0.35.

Die Aufgabe der vorliegenden Erfindung bestand darin, eine Rahstoffkombination aufzufinden, welche die Herstellung von hochdämpfenden Schaumstoffen gestattet; darunter versteht man Schaumstoffe, deren Verlustfaktoren mindestens einen Wert von 0,5 haben, bevorzugt aber Verlustfaktorwerte größer als 0,9 erreichen.The object of the present invention was to find a frame material combination which allows the production of highly damping foams; this means foams whose loss factors have at least a value of 0.5, but preferably reach loss factor values greater than 0.9.

Diese Aufgabe konnte Überraschenderweise, wie nachstehend erläutert, erfindungsgemäß gelöst werden. Gegenstand der Erfindung ist ein Verfahren zur Herstellung von kalthärtenden Polyurethan-Weichformschaumstoffen mit hervorragenden Dämpfungseigenschaften durch Umsetzung von Polyisocyanaten mit

  • a) mindestens einem mindestens zwei OH-Gruppen aufweisenden Polyether einer OH-Zahl von 20 bis 60 auf Basis von 75 bis 95 Gew.-% Propylenoxid und 5 bis 25 Gew.-% Ethylenoxid und
  • b) einem mindestens difuktionellen Polyether einer OH-Zahl von 150 bis 400 auf Basis Propylenoxid und ggf. Ethylenoxid.
in Gegenwart von Wasser und gegebenenfalls organischen Treibmitteln, Katalysatoren und Schaumstabilisatoren und gegebenenfalls weiteren Hilfs- und Zusatzmitteln, dadurch gekennzeichnet, daß zusätzlich zu den Polyolkomponenten a) und b) als weitere Polyetherkomponente
  • c) ein Polyether einer OH-Zahl von 20 bis 200 und einer von zwei bis sechs reichenden Funktionalität auf Basis von Propylenoxid und Ethylenoxid mit einem Ethylenoxidgehalt von über 50 Gew.-%, bezogen auf Propylenoxid und Ethylenoxid, in einer Konzentration von > 30% bezogen auf a) + b) + c)
verwendet wird.Surprisingly, as explained below, this object could be achieved according to the invention. The invention relates to a method for producing cold-curing flexible polyurethane foams with excellent damping properties by reacting polyisocyanates with
  • a) at least one polyether having at least two OH groups and having an OH number of 20 to 60 based on 75 to 95% by weight of propylene oxide and 5 to 25% by weight of ethylene oxide and
  • b) an at least difunctional polyether with an OH number of 150 to 400 based on propylene oxide and optionally ethylene oxide.
in the presence of water and optionally organic blowing agents, catalysts and foam stabilizers and optionally other auxiliaries and additives, characterized in that in addition to the polyol components a) and b) as a further polyether component
  • c) a polyether with an OH number of 20 to 200 and a functionality ranging from two to six based on propylene oxide and ethylene oxide with an ethylene oxide content of more than 50% by weight, based on propylene oxide and ethylene oxide, in a concentration of> 30% based on a) + b) + c)
is used.

Bevorzugt ist ein Verfahren, das dadurch gekennzeichnet ist, daß das Polyisocyanat mit der Polyetherkomponente c) in einer ersten Stufe zu einem Isocyanatgruppen aufweisenden Prepolymeren umgesetzt wird, welches dann anschließend mit den Polyol-Komponenten a) und b) in Gegenwart von Wasser und/oder organischen Treibmitteln, Katalysatoren und Schaumstabilisatoren und gegebenenfalls weiteren Hilfs- und Zusatzmitteln weiter umgesetzt wird.A process is preferred which is characterized in that the polyisocyanate is reacted with the polyether component c) in a first stage to form a prepolymer having isocyanate groups, which is then subsequently reacted with the polyol components a) and b) in the presence of water and / or organic blowing agents, catalysts and foam stabilizers and optionally further auxiliaries and additives.

Bevorzugt ist auch ein Verfahren, das darin besteht, daß das polyisocyanat mit der Polyetherkomponente a) in einer ersten Stufe zu einem Isocyanatgruppen aufweisenden Prepolymeren umgesetzt wird, welches dann anschließend mit den Komponenten c) und b) in Gegenwart von Wasser und/oder organischen Treibmitteln, Katalysatoren und Schaumstabilisatoren und gegebenenfalls weiteren Hilfs- und Zusatzmitteln weiter umgesetzt wird.Also preferred is a process which consists in reacting the polyisocyanate with the polyether component a) in a first stage to form a prepolymer containing isocyanate groups, which is then subsequently reacted with components c) and b) in the presence of water and / or organic blowing agents , Catalysts and foam stabilizers and optionally further auxiliaries and additives.

Bevorzugt ist ferner ein Verfahren, wonach die drei OH-Gruppen aufweisenden Komponenten a), b) und c) mit geringen Anteilen Polyisocyanat zu einem Hydroxylgruppen aufweisenden Prepolymeren umgesetzt werden, welches dann anschließend mit dem Polyisocyanat in Gegenwart von Wasser und/oder organischen Treibmitteln, Katalysatoren und Schaumstabilisatoren und gegebenenfalls weiteren Hilfs- und Zusatzmitteln weiter umgesetzt wird.Also preferred is a process according to which the three OH groups containing components a), b) and c) are reacted with small amounts of polyisocyanate to form a prepolymer containing hydroxyl groups, which is then subsequently reacted with the polyisocyanate in the presence of water and / or organic blowing agents, Catalysts and foam stabilizers and optionally other auxiliaries and additives is further implemented.

Vorzugsweise wird die Polyolkomponente b) in einer Menge von 10 bis 20 Gew.-%, bezogen auf die Polyolkomponenten a), b) und c), und die Polyetherkomponente c) in einer Menge von 30 bis 70 Gew.-%, bezogen auf die Polyetherkomponenten a), b) und c), verwendet.The polyol component b) is preferably in an amount of 10 to 20% by weight, based on the polyol components a), b) and c), and the polyether component c) in an amount of 30 to 70% by weight, based on the polyether components a), b) and c) used.

Die Polyetherkomponente c) weist vorzugsweise eine OH-Zahl von 25 bis 100 auf.The polyether component c) preferably has an OH number of 25 to 100.

Als Polyisocyanate werden erfindungsgemäß vorzugsweise aromatische Polyisocyanate eingesetzt. Die Polyetherkomponente a) weist bevorzugt erfindungsgemäß eine OH-Zahl von 25 bis 40 auf.According to the invention, aromatic polyisocyanates are preferably used as polyisocyanates. According to the invention, the polyether component a) preferably has an OH number of 25 to 40.

Schließlich ist bevorzugt, daß die OH-Gruppen aufweisende Komponente b) ein mindestens trifunktioneller Polyether einer OH-Zahl von 150 bis 400 auf Basis von Propylenoxid ist.Finally, it is preferred that component b) containing OH groups is an at least trifunctional polyether with an OH number of 150 to 400 based on propylene oxide.

Zur Herstellung der Polyurethan-Weichformschaumstoffe werden erfindungsgemäß als Ausgangskomponenten beispielsweise verwendet:

  • 1. Polyisocyanate vom Typ des Diphenylmethandiisocyanats und/oder des Toluylendiisocyanats, z. B. das 2,4- und 2,6-Toluylendiisocyanat, sowie beliebige Gemische dieser Isomeren ("TDI"); 4,4'-und/oder 2,4'-Diphenylmethandiisocyanat (MDI), Hexamethylendiisocyanat und/oder Isophorondiisocyanat, Polyphenylpolymethylen-polyisocyanate, wie sie durch Anilin-Formaldehyd-Kondensation und anschließende Phosgenierung hergestellt werden ("rohes MDI"), ferner durch Carbodiimidgruppen, Urethangruppen, Allophanatgruppen, Isocyanuratgruppen, Harnstoffgruppen oder Biuretgruppen modifizierte Polyisocyanate, die sich vom 2,4-und/oder 2,6-Toluylendiisocyanat bzw. vom 4,4'-und/oder 2,4'Dipenylmethandiisocyanat und/oder Hexamethylendiisocyanat und/oder Isophorondiisocyanat ableiten, ferner alkylsubstituierte MDI-Typen, wie sie beispielsweise in DE-OS 2 935 318, DE-OS 3 032 128 und DE-OS 3 032 358 beschrieben werden.
    Als erfindungsgemäß einzusetzende Polyisocyanate kommen vorzugsweise folgende MDI-Typen in Betracht:
    • a) Diphenylmethandiisocyanate im Gemisch mit Polyphenyl-polymethylen-polyisocyanaten, wobei der Anteil des Polyphenylpolymethylen-polyisocyanates 0 bis 40 Gew.-% und der Gehalt an Diphenylmethandiisocyanat-Isomeren 100 bis 60 Gew.-% betragen kann.
    • b) Urethanmodifizierte aromatische Di-/Poly-isocyanate mit einem NCO-Gehalt von 15 bis 30 Gew.-%, welche erhalten werden durch Umsetzung einer wie unter a) beschriebenen Mischung aus Diphenylmethandiisocyanaten und Polyphenyl-polymethylen-polyisocyanaten mit einer Hydroxylverbindung, gegebenenfalls auch mehreren Hydroxylverbindungen, deren Funktionalität 2 bis 6 beträgt.
    • c) Gemische der unter a) und/oder b) bezeichneten MDI-Produkte mit maximal 25 Gew.-% aliphatischen, cycloaliphatischen, heterocyclischen oder weiteren andersartigen aromatischen Polyisocyanaten, wie sie z.B. von W. Siefken in Justus Liebigs Annalen der Chemie, 562, Seiten 75 bis 136, beschrieben werden.
  • 2. Mischungen aus drei Polyolen mit jeweils mindestens zwei reaktionsfähigen OH-Gruppen.
    Bei der ersten Komponente a) handelt es sich um ein weichformschaumtypisches Polyetherpolyol, welches üblicherweise di- bis hexafunktionell ist, einen OH-Zahlbereich von 25 bis 60 abdeckt und endständig mit Ethylenoxid getippt ist.
    Bei der zweiten Komponente b) kommen meist Polyetherpolyole auf der Basis von Propylenoxid zur Anwendung. Polyester und Polyetherpolyole mit geringen Anteilen an Ethylenoxid sind ebenfalls geeignet. Neben den bevorzugt eingesetzten trifunktionellen Polyolen können auch lineare und höherfunktionelle Typen eingesetzt werden.
    Der dritte Bestandteil der Polyolabmischung ist ein Polyetherpolyol c) einer OH-Zahl von 20 bis 200, einer von zwei bis sechs reichenden Funktionalität und einem hohen Ethylenoxid-Anteil. Die weichformschaumtypischen Polyetherpolyole enthalten neben Propylenoxid Ethylenoxid in einer Konzentration, welche in der Regel 20 % nicht übersteigt. Für den erfindungsgemäßen hochdämpfenden Schaum ist aber ein Polyetherpolyol c) mit hohen Ethylenoxid-Anteilen (größer 50 Gew.-%) Voraussetzung. Um die gewünschte hohe Dämpfung zu erreichen, muß die notwendige Konzentration dieses Polyols 30 %, bezogen auf die Polyolkomponenten a), b) und c), überschreiten.
  • 3. Gegebenenfalls Verbindungen mit mindestens zwei gegenüber Isocyanaten reaktionsfähigen Wasserstoffatomen und einem Molekulargewicht von 32 bis 399. Man versteht hierunter Hydroxylgruppen und/oder Aminogruppen und/oder Thiolgruppen und/oder Carboxylgruppen aufweisende Verbindungen, vorzugsweise Hydroxylgruppen und/oder Aminogruppen aufweisende Verbindungen, die als Kettenverlängerungsmittel oder Vernetzungsmittel dienen. Diese Verbindungen weisen in der Regel 2 bis 8, vorzugsweise 2 bis 4, gegenüber Isocyanaten reaktionsfähige Wasserstoffatome auf. Beispiele hierfür werden in der DE-OS 2 832 253, Seiten 10 bis 20, beschrieben.
  • 4. Wasser als Treibmittel, vorzugsweise in einer Menge von 1 bis 4 Gew.-Teilen pro 100 Gew.-Teile Polyolmischung a)+b)+c).
  • 5. Gegebenenfalls Hilfs- und Zusatzmittel wie
    • a) leicht flüchtige organische Substanzen als weitere Treibmittel,
    • b) Reaktionsbeschleuniger und Reaktionsverzögerer der an sich bekannten Art in der an sich üblichen Menge,
    • c) oberflächenaktive Zusatzstoffe, wie Emulgatoren und Schaumstabilisatoren,
      ferner Zellregler der an sich bekannten Art wie Paraffine oder Fettalkohole oder Dimethylpolysiloxane sowie Pigmente oder Farbstoffe und Flammschutzmittel der an sich bekannten Art, z.B. Trichlorethylphosphat, Trikresylphosphat, ferner Stabilisatoren gegen Alterungs- und Witterungseinflüsse, Weichmacher und fungistatisch und bakterostatisch wirkende Substanzen sowie Füllstoffe wie Bariumsulfat, Kieselgut, Ruß oder Schlämmkreide.
To produce the flexible polyurethane foams, the following are used as starting components according to the invention, for example:
  • 1. Polyisocyanates of the diphenylmethane diisocyanate and / or tolylene diisocyanate type, e.g. B. the 2,4- and 2,6-tolylene diisocyanate, and any mixtures of these isomers ("TDI");4,4'-and / or 2,4'-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate and / or isophorone diisocyanate, polyphenylpolymethylene polyisocyanates as produced by aniline-formaldehyde condensation and subsequent phosgenation ("crude MDI"), further by Carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups, modified polyisocyanates derived from 2,4- and / or 2,6-tolylene diisocyanate or from 4,4'- and / or 2,4'-dipenylmethane diisocyanate and / or hexamethylene diisocyanate and / or derive isophorone diisocyanate, furthermore alkyl-substituted MDI types, as described for example in DE-OS 2 935 318, DE-OS 3 032 128 and DE-OS 3 032 358.
    The following MDI types are preferably suitable as polyisocyanates to be used according to the invention:
    • a) Diphenylmethane diisocyanates in a mixture with polyphenyl polymethylene polyisocyanates, the proportion of the polyphenylpolymethylene polyisocyanate being 0 to 40% by weight and the content of diphenylmethane diisocyanate isomers being 100 to 60% by weight.
    • b) Urethane-modified aromatic di- / poly-isocyanates with an NCO content of 15 to 30% by weight, which are obtained by reacting a mixture of diphenylmethane diisocyanates and polyphenylpolymethylene polyisocyanates as described under a) with a hydroxyl compound, if appropriate also several hydroxyl compounds, the functionality of which is 2 to 6.
    • c) Mixtures of the MDI products described under a) and / or b) with a maximum of 25% by weight of aliphatic, cycloaliphatic, heterocyclic or other different aromatic polyisocyanates, as described, for example, by W. Siefken in Justus Liebigs Annalen der Chemie, 562, Pages 75 to 136.
  • 2. Mixtures of three polyols, each with at least two reactive OH groups.
    The first component a) is a soft molded foam-typical polyether polyol, which is usually di- to hexafunctional, covers an OH number range from 25 to 60 and is end-typed with ethylene oxide.
    The second component b) usually uses polyether polyols based on propylene oxide. Polyesters and polyether polyols with low levels of ethylene oxide are also suitable. In addition to the preferred trifunctional polyols, linear and higher-functional types can also be used.
    The third component of the polyol blend is a polyether polyol c) having an OH number of 20 to 200, one of two to six functionalities and a high proportion of ethylene oxide. In addition to propylene oxide, the soft molded foam-typical polyether polyols contain ethylene oxide in a concentration which generally does not exceed 20%. However, a polyether polyol c) with high proportions of ethylene oxide (greater than 50% by weight) is a prerequisite for the highly damping foam according to the invention. In order to achieve the desired high attenuation, the necessary concentration of this polyol must exceed 30%, based on the polyol components a), b) and c).
  • 3. If appropriate, compounds having at least two isocyanate-reactive hydrogen atoms and a molecular weight of 32 to 399. This is taken to mean hydroxyl groups and / or amino groups and / or compounds containing thiol groups and / or carboxyl groups, preferably compounds having hydroxyl groups and / or amino groups, which act as chain extenders or crosslinking agents. These compounds generally have 2 to 8, preferably 2 to 4, hydrogen atoms which are reactive toward isocyanates. Examples of this are described in DE-OS 2 832 253, pages 10 to 20.
  • 4. Water as blowing agent, preferably in an amount of 1 to 4 parts by weight per 100 parts by weight of polyol mixture a) + b) + c).
  • 5. If necessary, auxiliaries and additives such as
    • a) volatile organic substances as further blowing agents,
    • b) reaction accelerators and reaction retarders of the type known per se in the amount customary per se,
    • c) surface-active additives, such as emulsifiers and foam stabilizers,
      cell regulators of the type known per se, such as paraffins or fatty alcohols or dimethylpolysiloxanes, as well as pigments or dyes and flame retardants of the type known per se, for example trichloroethyl phosphate, tricresyl phosphate, stabilizers against aging and weathering, plasticizers and fungistatic and bacterostatic substances and fillers such as barium sulfate, Kieselgut, soot or chalk.

Diese gegebenenfalls mitzuverwendenden Hilfs- und Zusatzstoffe werden beispielsweise in der DE-OS 2 732 292, Seiten 21-24, beschrieben.These auxiliary substances and additives, which may also be used, are described, for example, in DE-OS 2 732 292, pages 21-24.

Weitere Beispiele von gegebenenfalls erfindungsgemäß mitzuverwendenden oberflächenaktiven Zusatzstoffen und Schaumstabilisatoren sowie Zellreglern, Reaktionsverzögerern, Stabilisatoren, flammhemmenden Substanzen, Weichmachern, Farbstoffen und Füllstoffen sowie fungistatisch und bakteriostatisch wirksamen Substanzen sowie Einzelheiten über Verwendungs- und Wirkungsweise dieser Zusatzmittel sind im Kunststoff-Handbuch, Band VII, herausgegeben von Vieweg und Höchtlen, Carl-Hanser-Verlag, München 1966, z B. auf den Seiten 103-113 beschrieben.Further examples of surface-active additives and foam stabilizers to be used according to the invention, as well as cell regulators, reaction retarders, stabilizers, flame-retardant substances, plasticizers, dyes and fillers, as well as fungistatic and bacteriostatic substances, as well as details on the use and mode of action of these additives are given in the Plastics Manual, Volume VII by Vieweg and Höchtlen, Carl-Hanser-Verlag, Munich 1966, e.g. on pages 103-113.

Durchführung des erfindungsgemäßen Verfahrens:
Die Reaktionskomponenten werden erfindungsgemäß nach dem an sich bekannten Einstufenverfahren, dem Präpolymerverfahren oder dem Semipräpolymerverfahren zu Umsetzung gebracht, wobei man sich oft maschineller Einrichtungen bedient, z.B. solcher, die in der US-Patentschrift 2 764 565 beschrieben werden. Einzelheiten über Verarbeitungseinrichtungen, die auch erfindungsgemäß infrage kommen, werden in Kunststoff-Handbuch, Band VII, herausgegeben von Vieweg und Höchtlen, Carl-Hanser-Verlag, München 1966, z. B. auf den Seiten 121-205, beschrieben.Implementation of the method according to the invention:
According to the invention, the reaction components are reacted according to the one-step process, the prepolymer process or the semi-prepolymer process, which are known per se, machine equipment often being used, for example those described in US Pat. No. 2,764,565. Details about processing devices, which are also suitable according to the invention, are found in Kunststoff-Handbuch, Volume VII, edited by Vieweg and Höchtlen, Carl-Hanser-Verlag, Munich 1966, e.g. B. on pages 121-205.

Die Umsetzung aller Komponenten erfolgt erfindungsgemäß bei einer Kennzahl über 70, vorzugsweise bei einer Kennzahl von 70 bis 115.According to the invention, all components are implemented with a key figure above 70, preferably with a key figure from 70 to 115.

Die Kennzahl, ein bei der Herstellung von Polyurethanschaumstoffen sehr häufig verwendeter Begriff, sagt etwas über den Vernetzungsgrad eines Schaumstoffs aus. Es ist Gepflogenheit, denjenigen Schaumstoff als mit der Kennzahl 100 gefertigt zu betrachten, bei welchem die den stöchiometrischen Verhältnissen entsprechende, bzw. die theoretisch notwendige Menge an Isocyanat benutzt wurde. Mit Hilfe der Kennzahl ist es also möglich, den Grad der Unter- oder Übervernetzung näher zu definieren. Die Kennzahl errechnet sich nach der allgemeinen Formel wie folgt:

Figure imgb0001
The key figure, a term used very often in the production of polyurethane foams, says something about the degree of crosslinking of a foam. It is customary to consider that foam with the code number 100, in which the stoichiometric ratio or the theoretically necessary amount of isocyanate was used. With the help of the key figure it is possible to define the degree of under- or over-networking in more detail. The key figure is calculated according to the general formula as follows:
Figure imgb0001

Erfindungsgemäß wird die Verschäumung in geschlossenen Formen durchgeführt. Dabei wird das Reaktionsgemisch in eine Form eingetragen. Als Formmaterial kommt Metall, z.B. Aluminium oder Kunststoff, z.B. Epoxidharz, infrage. In der Form schäumt das schäumfähige Reaktionsgemisch auf und bildet den Formkörper. Erfindungsgemäß kann man in diesem Zusammenhang so vorgehen, daß man in die Form so viel schaumfähiges Reaktionsgemisch einträgt, daß der gebildete Schaumstoff die Form gerade ausfüllt. Man kann aber auch so arbeiten, daß man mehr schaumfähiges Reaktionsgemisch in die Form einträgt, als zur Auffüllung des Forminneren mit Schaumstoff notwendig ist. Im letztgenannten Fall wird somit unter "over-charging" gearbeitet; eine derartige Verfahrensweise ist z.B. aus den US-Patentschriften 3 178 490 und 3 182 104 bekannt.According to the invention, the foaming is carried out in closed molds. The reaction mixture is introduced into a mold. Metal, for example aluminum or plastic, for example epoxy resin, can be used as the molding material. The foamable reaction mixture foams in the mold and forms the shaped body. According to the invention, one can proceed in this connection in such a way that so much foamable reaction mixture is introduced into the mold that the foam formed just fills the mold. However, it is also possible to work by adding more foamable reaction mixture to the mold than is necessary to fill the interior of the mold with foam. In the latter case, "over-charging" is used; such a procedure is known, for example, from US Pat. Nos. 3,178,490 and 3,182,104.

Die günstigen Eigenschaften der erfindungsgemäßen Polyurethanschäume werden durch die besondere Zusammensetzung der Polyolkomponente erreicht. Es sind zwar bestimmte Abmischungen (z.B. Beispiel 1) instabil und entmischen sich innerhalb von Stunden. Lagerstabile A/B-Systeme konnten aber durch eine vorgelagerte Prepolymerisierungsreaktion erhalten werden. Diese Systeme haben verarbeitungstechnische Vorteile. Drei Prepolymerisierungsverfahren wurden angewendet, um eine Entmischung der Polyolkomponente zu verhindern.

  • Herstellung eines NCO-haltigen Prepolymeren durch Vorreaktion von Anteilen oder von der Gesamtmenge des Polyethers c) im Isocyanat. Es haben sich Prepolymere bewährt, deren NCO-Gehalt zwischen 10 und 20 % liegt.
  • Herstellung eines NCO-haltigen Prepolymeren durch Vorreaktion des Weichformschaumpolyols a) mit dem Isocyanat. Die Komponente b) ist mit dem ethylenoxidreichen Polyol mischbar; aus diesem Grund lassen sich stabile Formulierungen herstellen.
  • Herstellung eines OH-funktionellen Prepolymers durch Umsetzung der Polyolmischung mit geringen Teilen Isocyanat. Die Vorvernetzung verhindert die Phasenseparierung. Die zugegebene Isocyanatmenge wird so dosiert, daß einerseits die Viskosität des Polyols in einem verarbeitbaren Rahmen bleibt und andererseits eine Entmischung vermieden wird.
The favorable properties of the polyurethane foams according to the invention are achieved by the special composition of the polyol component. Certain mixtures (eg example 1) are unstable and separate within hours. Storage-stable A / B systems could, however, be obtained by an upstream prepolymerization reaction. These systems have processing advantages. Three prepolymerization methods were used to prevent segregation of the polyol component.
  • Production of an NCO-containing prepolymer by prereaction of parts or of the total amount of polyether c) in the isocyanate. Prepolymers whose NCO content is between 10 and 20% have proven successful.
  • Production of an NCO-containing prepolymer by pre-reaction of the flexible foam polyol a) with the isocyanate. Component b) is miscible with the ethylene oxide-rich polyol; for this reason stable formulations can be produced.
  • Production of an OH-functional prepolymer by reacting the polyol mixture with small parts of isocyanate. Pre-crosslinking prevents phase separation. The amount of isocyanate added is metered in such a way that on the one hand the viscosity of the polyol remains within a processable range and on the other hand segregation is avoided.

Die erfindungsgemäß hergestellten Weichformschaumstoffe liegen in einem Rohdichtebereich von 25 bis 250 kg/m³, wobei Verlustfaktoren von über 0,8 ohne den Zusatz von anorganischen und/oder organischen Füllstoffen erreicht werden. Die Polyurethanschaumstoffe können in Abhängigkeit von der Kennzahl und Treibmittelgehalt weich bis hart eingestellt werden, ohne ihre Flexibilität zu verlieren.The flexible molded foams produced according to the invention are in a bulk density range of 25 to 250 kg / m 3, loss factors of over 0.8 being achieved without the addition of inorganic and / or organic fillers. The polyurethane foams can be soft to hard depending on the key figure and blowing agent content, without losing their flexibility.

Als mögliche Anwendungen der erfindungsgemäß hergestellten hochdämpfenden Schaumstoffe kommen z.B. in Frage:

  • Als Feder in Masse-Feder-Systemen (Akustik)
    Heute gefertigte Automobile werden häufig zur Geräuschminderung im Fahrgastraum mit Teppichbodenkonstruktionen, die aus einem Verbund aus Textilbelag, Schwermatte (Masse) und PU-Schaum (Feder) bestehen. Hochdämpfender Schaum kann die Resonanzeinbrüche bei niedrigen Frequenzen verhindern und wirkt gleichzeitig als Schallabsorptionsdedium.
  • Schallabsorption (Akustik)
    Ein hoher Verlustfaktor verbessert die guten Dämpfungseigenschaften von PU-Schaumstoffen.
  • Energieabsorption (z.B. Aufprallenergie)
    Die geringe Rückprallelastizität der erfindungsgemäß hergestellten Schaumstoffe (vgl. Beispiel 1) beweist die große Energieabsorption der erfindungsgemäß hergestellten Schaumstoffe.
Possible applications of the highly damping foams produced according to the invention are, for example:
  • As a spring in mass-spring systems (acoustics)
    Automobiles manufactured today are often used to reduce noise in the passenger compartment with carpeted constructions that consist of a composite of textile covering, heavy mat (mass) and PU foam (spring). Highly damping foam can prevent resonance dips at low frequencies and at the same time acts as a sound absorption medium.
  • Sound absorption (acoustics)
    A high loss factor improves the good damping properties of PU foams.
  • Energy absorption (e.g. impact energy)
    The low rebound resilience of the foams produced according to the invention (cf. Example 1) proves the high energy absorption of the foams produced according to the invention.

Beispiel 1example 1

Herstellung eines Polyurethanschaumstoffs aus:

Figure imgb0002
Production of a polyurethane foam from:
Figure imgb0002

B-KomponenteB component

MDI 85/20:
Gemisch aus 65 % 4,4' und 20 % 2,4'-Diisocyanatodiphenylmethan und 15 % höherfunktionellen Polyisocyanaten der Diphenylmethanreihe.MDI 85/20:
Mixture of 65% 4,4 'and 20% 2,4'-diisocyanatodiphenylmethane and 15% higher functional polyisocyanates of the diphenylmethane series.

100 Gew.-Teile der A-Komponente werden mit 45,5 Gew.-Teilen der B-Komponente intensiv vermischt (Kennzahl 86). Die Reaktionsmischung wird in eine auf 50°C erwärmte, quaderförmige Metallform eingebracht, die Form wird mit einem Metalldeckel geschlossen und die Reaktionsmischung schäumt auf.100 parts by weight of the A component are mixed intensively with 45.5 parts by weight of the B component (code 86). The reaction mixture is introduced into a cuboid metal mold heated to 50 ° C., the mold is closed with a metal lid and the reaction mixture foams.

Der sich ergebende Polyurethan-Weichformschaumstoff hat folgende mechanische Eigenschaften: Rohdichte (DIN 53 420) 81 kg/m³ Zugfestigkeit (DIN 53 571) 95 kPa Bruchdehnung (DIN 53 571) 140 % Stauchhärte 40 % (DIN 53 577) 4,4 kPa Druckverformungsrest (50 %, 22 h, 70°C, DIN 53 572) 2,9 % Rückprallelastizität (DIN 53 573) 14 % Verlustfaktor (bestimmt nach dem Hubschwingungsverfahren) 0,88 The resulting flexible polyurethane foam has the following mechanical properties: Gross density (DIN 53 420) 81 kg / m³ Tensile strength (DIN 53 571) 95 kPa Elongation at break (DIN 53 571) 140% Compression hardness 40% (DIN 53 577) 4.4 kPa Compression set (50%, 22 h, 70 ° C, DIN 53 572) 2.9% Rebound resilience (DIN 53 573) 14% Loss factor (determined according to the stroke vibration method) 0.88

Beispiel 2Example 2 A-KomponenteA component

25 Gew.-Teile Polyol A
15 Gew.-Teile Polyol B
60 Gew.-Teile Polyol C
2,5 Gew.-Teile Wasser
0,3 Gew.-Teile Dimethylethanolamin
0,6 Gew.-Teile Triethylendiamin (33 Gew.-% in Dipropylenglykol)
0,83 Gew.-Teile Bis-dimethylaminopropyl-amin
1,0 Gew.-Teile Triethanolamin
1,0 Gew.-Teile Silikonstabilisator B 4900 der Fa. Goldschmidt AG, Essen.25 parts by weight of polyol A
15 parts by weight of polyol B
60 parts by weight of polyol C
2.5 parts by weight of water
0.3 part by weight of dimethylethanolamine
0.6 parts by weight of triethylene diamine (33% by weight in dipropylene glycol)
0.83 parts by weight of bis-dimethylaminopropylamine
1.0 part by weight of triethanolamine
1.0 part by weight of silicone stabilizer B 4900 from Goldschmidt AG, Essen.

B-KomponenteB component

Abmischung aus 40 % TDI 65 und 60 % MDI roh
100 Gew.-Teile der A-Komponente werden mit 43,1 Gew.-Teilen der B-Komponente intensiv vermischt (Kennzahl 90). Die Reaktionsmischung wird in eine auf 50°C erwärmte, quaderförmige Metallform eingebracht, die Form wird mit einem Metalldeckel geschlossen und die Reaktionsmischung schäumt auf.Mixture of 40% TDI 65 and 60% MDI raw
100 parts by weight of the A component are mixed intensively with 43.1 parts by weight of the B component (code number 90). The reaction mixture is introduced into a cuboid metal mold heated to 50 ° C., the mold is closed with a metal lid and the reaction mixture foams.

Eigenschaften des Polyurethanweichschaumstoffs: Rohdichte (DIN 53 420) 78 kg/m³ Stauchhärte 40 % (DIN 53 571) 10,1 kPa Verlustfaktor (bestimmt nach dem Hubschwingverfahren) 0,64 Properties of the flexible polyurethane foam: Gross density (DIN 53 420) 78 kg / m³ Compression hardness 40% (DIN 53 571) 10.1 kPa Loss factor (determined according to the lift swing method) 0.64

Beispiel 3Example 3

Herstellung eines Polyurethanweichschaumstoffs aus:Production of a flexible polyurethane foam from:

A-KomponenteA component

25 Gew.-Teile Polyol A
15 Gew.-Teile Polyol B
60 Gew.-Teile Polyol C
2,5 Gew.-Teile Wasser
0,3 Gew.-Teile Dimethylethanolamin
0,6 Gew.-Teile Triethylendiamin (33 Gew.-% in Dipropylenglykol)
0,83 Gew.-Teile Bis-dimethylaminopropyl-amin
1,0 Gew.-Teile Silikonstabilisator B 4900 der Fa. Goldschmidt AG, Essen.25 parts by weight of polyol A
15 parts by weight of polyol B
60 parts by weight of polyol C
2.5 parts by weight of water
0.3 part by weight of dimethylethanolamine
0.6 parts by weight of triethylene diamine (33% by weight in dipropylene glycol)
0.83 parts by weight of bis-dimethylaminopropylamine
1.0 part by weight of silicone stabilizer B 4900 from Goldschmidt AG, Essen.

B-KomponenteB component

Abmischung aus 90 % durch Teilurethanisierung und Teilallophanatisierung modifiziertes TDI und 10 % MDI roh mit einem NCO-Gehalt von etwa 40 %.Mixture of 90% TDI modified by partial urethanization and partial allophanatization and 10% raw MDI with an NCO content of approximately 40%.

Aus 100 Gew.-Teilen Komponente A und 41,1 Gew.-Teilen Komponente B (Kennzahl 90) wird wie in Beispiel 1 ein Formteil mit folgenden Eigenschaften hergestellt: Rohdichte (DIN 53 420) 82 kg/m³ Stauchhärte 40 % (DIN 53 571) 3,9 kPa Verlustfaktor (bestimmt nach dem Hubschwingverfahren) 0,57 A molded part with the following properties is produced from 100 parts by weight of component A and 41.1 parts by weight of component B (code number 90) as in Example 1: Gross density (DIN 53 420) 82 kg / m³ Compression hardness 40% (DIN 53 571) 3.9 kPa Loss factor (determined according to the lift swing method) 0.57

Beispiel 4Example 4

Die in den Beispielen 1 bis 3 aufgeführten Formulierungen sind phaseninstabil. Durch Prepolymerisierung des Weichformschaumpolyols (Polyetherkomponente a)) wird in Beispiel 4 eine phasenstabile Formulierung möglich.
40 Gew.-Teile eines mit Sorbit gestarteten Polyoxypropyloxyethylenpolyols einer OH-Zahl von 100 und 82,2 % endständigen Oxyethylengruppen (Polyol D).
40 Gew.-Teile Polyol C
20 Gew.-Teile Polyol B
3,33 Gew.-Teile Wasser
0,40 Gew.-Teile Triethylendiamin (33 Gew.-% in Dipropylenglykol)
0,67 Gew.-Teile Bis-dimethylaminopropyl-amin
0,40 Gew.-Teile Bis-dimethylaminopropyl-ether
0,27 Gew.-Teile Silikonstabilisator B 4900 (Goldschmidt AG, Essen)The formulations listed in Examples 1 to 3 are phase-unstable. In Example 4, a phase-stable formulation is possible by prepolymerizing the flexible foam polyol (polyether component a)).
40 parts by weight of a sorbitol-started polyoxypropyloxyethylene polyol with an OH number of 100 and 82.2% terminal oxyethylene groups (polyol D).
40 parts by weight of polyol C
20 parts by weight of polyol B
3.33 parts by weight of water
0.40 part by weight of triethylene diamine (33% by weight in dipropylene glycol)
0.67 parts by weight of bis-dimethylaminopropylamine
0.40 part by weight of bis-dimethylaminopropyl ether
0.27 part by weight of silicone stabilizer B 4900 (Goldschmidt AG, Essen)

B-KomponenteB component

Durch Umsetzung von 80 Gew.-Teilen MDI 85/20 mit 20 Gew.-Teilen Polyol A entsteht ein Semiprepolymeres mit einem NCO-Gehalt von etwa 25 %. Die Reaktion wird bei Raumtemperatur unter ständigem Rühren ausgeführt. Nach 24 Stunden ist die Reaktion abgeschlossen.The reaction of 80 parts by weight of MDI 85/20 with 20 parts by weight of polyol A results in a semiprepolymer with an NCO content of about 25%. The reaction is carried out at room temperature with constant stirring. The reaction is complete after 24 hours.

Aus 100 Gew.-Teilen Komponente A und 91,5 Gew.-Teilen Komponente B (Kennzahl 70) wird wie in Beispiel 1 ein Formteil mit folgenden Eigenschaften hergestellt: Rohdichte (DIN 53 420) 92 kg/m³ Stauchhärte 40 % (DIN 53 571) 5,04 kPa Verlustfaktor (bestimmt nach dem Hubschwingverfahren) 1,09 A molded part with the following properties is produced from 100 parts by weight of component A and 91.5 parts by weight of component B (code number 70) as in Example 1: Gross density (DIN 53 420) 92 kg / m³ Compression hardness 40% (DIN 53 571) 5.04 kPa Loss factor (determined according to the lift swing method) 1.09

Beispiel 5Example 5

Herstellung eines Polyurethanweichschaumstoffs ausManufacture of a flexible polyurethane foam

A-KomponenteA component

102 Gew.-Teile eines OH-funktionellen Prepolymeren, welches wie folgt hergestellt wird. Aus
25 Gew.-Teilen Polyol A
15 Gew.-Teilen Polyol B
60 Gew.-Teilen Polyol C und
2 Gew.-Teilen MDI 85/20
wird unter ständigem Rühren eine über mehrere Wochen phasenstabile Flüssigkeit hergestellt (Reaktionszeit 24 h).
2,5 Gew.-Teile Wasser
0,6 Gew.-Teile Triethylendiamin (33 Gew.-% in Dipropylenglykol)
0,1 Gew.-Teile Bis-dimethylaminopropylether
1,0 Gew.-Teile Methyldicyclohexylamin
0,6 Gew.-Teile PU-Vernetzer 56 der Bayer AG
0,4 Gew.-Teile Silikonstabilisator B 4900 der Fa. Goldschmidt AG, Essen102 parts by weight of an OH-functional prepolymer, which is produced as follows. Out
25 parts by weight of polyol A
15 parts by weight of polyol B
60 parts by weight of polyol C and
2 parts by weight of MDI 85/20
a liquid that is phase stable for several weeks is produced with constant stirring (reaction time 24 h).
2.5 parts by weight of water
0.6 parts by weight of triethylene diamine (33% by weight in dipropylene glycol)
0.1 part by weight of bis-dimethylaminopropyl ether
1.0 part by weight of methyldicyclohexylamine
0.6 parts by weight of PU crosslinker 56 from Bayer AG
0.4 part by weight of silicone stabilizer B 4900 from Goldschmidt AG, Essen

B-KomponenteB component

MDI 85/20
100 Gew.-Teile der A-Komponente werden mit 43,8 Gew.-Teilen der B-Komponente intensiv vermischt (Kennzahl 80) und wie in Beispiel 1 in eine Metallform eingebracht.MDI 85/20
100 parts by weight of the A component are mixed intensively with 43.8 parts by weight of the B component (code number 80) and introduced into a metal mold as in Example 1.

Eigenschaftsniveau des Polyurethanschaumstoffs: Rohdichte (DIN 53 420) 73,4 kg/m³ Stauchhärte 40 % (DIN 53 571) 4,53 kPa Verlustfaktor (bestimmt nach dem Hubschwingverfahren) 1,01 Property level of the polyurethane foam: Gross density (DIN 53 420) 73.4 kg / m³ Compression hardness 40% (DIN 53 571) 4.53 kPa Loss factor (determined according to the lift swing method) 1.01

Claims (10)

  1. A process for the production of cold-curing flexible moulded polyurethane foams having excellent damping properties by reaction of polyisocyanates with
    a) at least one polyether containing at least two OH groups and having an OH value of 20 to 60 based on 75 to 95% by weight propylene oxide and 5 to 25% by weight ethylene oxide and
    b) an at least difunctional polyether having an OH value of 150 to 400 based on propylene oxide and optionally ethylene oxide
    in the presence of water and optionally organic blowing agents, catalysts and foam stabilizers and optionally other auxiliaries and additives, characterized in that, in addition to polyether components a) and b),
    c) a polyether having an OH value of 20 to 200 and a functionality of two to six based on propylene oxide and ethylene oxide with an ethylene oxide content of more than 50% by weight, based on propylene oxide and ethylene oxide, in a concentration of > 30%, based on a)+b)+c),
    is used as a further polyether component, the reaction of all the components taking place at an index of 70 to 115.
  2. A process as claimed in claim 1, characterized in that the polyisocyanate is reacted with the polyether component c) in a first stage to form a prepolymer containing isocyanate groups which is then itself reacted with the polyol components a) and b) in the presence of water and/or organic blowing agents, catalysts and foam stabilizers and, optionally, other auxiliaries and additives.
  3. A process as claimed in claims 1 and 2, characterized in that the polyisocyanate is reacted with the polyether component a) in a first stage to form a prepolymer containing isocyanate groups which is then itself reacted with the components c) and b) in the presence of water and/or organic blowing agents, catalysts and foam stabilizers and, optionally, other auxiliaries and additives.
  4. A process as claimed in claims 1 to 3, characterized in that the three OH-functional components a), b) and c) are reacted with small amounts of polyisocyanate to form a prepolymer containing hydroxyl groups which is then itself reacted with the polyisocyanate in the presence of water and/or organic blowing agents, catalysts and foam stabilizers and, optionally, other auxiliaries and additives.
  5. A process as claimed in claims 1 to 4, characterized in that the polyol component b) is used in a quantity of 10 to 20% by weight, based on the polyether components a), b) and c).
  6. A process as claimed in claims 1 to 5, characterized in that the polyether component c) is used in a quantity of 30 to 70% by weight, based on the polyol components a), b) and c).
  7. A process as claimed in claims 1 to 6, characterized in that the polyether component c) has an OH value of 25 to 100.
  8. A process as claimed in claims 1 to 7, characterized in that aromatic polyisocyanates are used as the polyisocyanates.
  9. A process as claimed in claims 1 to 8, characterized in that the polyether component a) has an OH value of 25 to 40.
  10. A process as claimed in claims 1 to 9, characterized in that the OH-functional component b) is an at least trifunctional polyether having an OH value of 150 to 400 based on propylene oxide.
EP89102703A 1988-03-01 1989-02-17 Process for the preparation of cold-hardening flexible polyurethane foams having excellent deadening properties Expired - Lifetime EP0331941B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3806476A DE3806476A1 (en) 1988-03-01 1988-03-01 METHOD FOR PRODUCING CALINARY POLYURETHANIC SOFT FORMULA MATERIALS WITH EXCELLENT DAWNING PROPERTIES
DE3806476 1988-03-01

Publications (2)

Publication Number Publication Date
EP0331941A1 EP0331941A1 (en) 1989-09-13
EP0331941B1 true EP0331941B1 (en) 1993-05-19

Family

ID=6348478

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89102703A Expired - Lifetime EP0331941B1 (en) 1988-03-01 1989-02-17 Process for the preparation of cold-hardening flexible polyurethane foams having excellent deadening properties

Country Status (7)

Country Link
US (1) US5063253A (en)
EP (1) EP0331941B1 (en)
JP (1) JP2587290B2 (en)
AU (1) AU624602B2 (en)
CA (1) CA1319786C (en)
DE (2) DE3806476A1 (en)
ES (1) ES2054895T3 (en)

Families Citing this family (65)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5171759A (en) * 1988-07-12 1992-12-15 Arco Chemical Technology, L.P. Polymer polyol compositions and their use in the preparation of polyurethane foams
US4980445A (en) * 1989-01-17 1990-12-25 The Dow Chemical Company Thermoplastic polyurethanes
DE3942330A1 (en) * 1989-12-21 1991-06-27 Basf Ag METHOD FOR THE PRODUCTION OF FLEXIBLE POLYURETHANE SOFT FOAMS WITH VISCOELASTIC, BODY SOUND ABSORBING PROPERTIES AND POLYOXYALKYLENE-POLYOL BLENDS TO BE USED THEREFOR
DE4001249A1 (en) * 1990-01-18 1991-07-25 Bayer Ag Cold formable open cell rigid polyurethane foam prodn. - from specified poly:ol component and crude MDI, used for car canopy
DE4007330A1 (en) * 1990-03-08 1991-09-12 Bayer Ag METHOD FOR THE PRODUCTION OF URETHANE, UREA AND BIURET GROUPS IN THE ESSENTIAL CLOSED CELLS GROUP AND USE THEREOF
IT1246042B (en) * 1990-11-16 1994-11-07 Montedipe Srl FLEXIBLE POLYURETHANE FOAMS AND PROCEDURE FOR THEIR PREPARATION
GB9028096D0 (en) * 1990-12-27 1991-02-13 Ici Plc Isocyanate-reactive compositions
DE4129666C2 (en) * 1991-09-06 1996-12-12 Stankiewicz Gmbh Process for the production of a viscoelastic damping foam with an adhesive surface
GB9126741D0 (en) * 1991-12-17 1992-02-12 Ici Plc Polyurethane foams
EP0547765B1 (en) 1991-12-17 1997-06-11 Imperial Chemical Industries Plc Polyurethane foams
GB9126740D0 (en) * 1991-12-17 1992-02-12 Ici Plc Polyol compositions
US6376698B1 (en) 1991-12-17 2002-04-23 Imperial Chemical Industries Plc Prepolymers
DE4204395A1 (en) * 1992-02-14 1993-08-19 Bayer Ag METHOD FOR THE PRODUCTION OF CALTENING POLYURETHANIC SOFT FORMULA SUBSTANCES
TW293827B (en) * 1992-04-20 1996-12-21 Takeda Pharm Industry Co Ltd
US5686502A (en) * 1992-07-01 1997-11-11 Polyfoam Products, Inc. Water blown, hydrophilic, open cell polyurethane foams, method of making such foams and articles made therefrom
US5397609A (en) * 1993-03-11 1995-03-14 Chapman; Jeffrey A. Carvable novelty articles and methods
US5378733A (en) * 1993-04-09 1995-01-03 Seaward International, Inc. Sound attenuating polymer composites
US5773483A (en) * 1993-04-13 1998-06-30 Imperial Chemical Industries Plc Process for preparing a flexible foam
EP0622388B2 (en) * 1993-04-26 2001-04-11 Takeda Chemical Industries, Ltd. Method of producing open cell rigid polyurethane foam
GB9311838D0 (en) * 1993-06-08 1993-07-28 Ici Plc Process for making flexible foams
CA2132595C (en) * 1993-09-22 1999-03-16 Thomas L. Fishback Polyol composition having good flow and water blown rigid polyurethane foams made thereby having good dimensional stability
US5478494A (en) * 1993-09-22 1995-12-26 Basf Corporation Polyol composition having good flow and formic acid blown rigid polyurethane foams made thereby having good dimensional stability
US6521674B1 (en) 1993-10-01 2003-02-18 Carpenter Co. Latex-like flexible polyurethane foam and process for making same
TW358815B (en) * 1994-06-16 1999-05-21 Huntsman Ici Chem Llc Process for preparing a flexible polyurethane foam
US5484820A (en) * 1994-08-05 1996-01-16 The Dow Chemical Company Polyurethane foam for packaging applications
US5900442A (en) * 1995-05-12 1999-05-04 Imperial Chemical Industries Plc Flexible polyurethane foams
US5596059A (en) * 1995-07-26 1997-01-21 Arco Chemical Technology, L.P. Polyether polyols suitable for mflexible polyurethane foam prepared by co-initiation of aqueous solutions of solid polyhydroxyl initiators
JP3112259B2 (en) * 1996-10-22 2000-11-27 東海化成工業株式会社 Shock absorbing headrest
DE19649829A1 (en) * 1996-12-02 1998-06-04 Bayer Ag Flexible polyurethane foams and a process for their production
ID22640A (en) * 1997-03-25 1999-12-02 Huntsman Ici Chem Llc PROCESS OF MAKING FLEXIBLE POLYURETHANE FOAM
JP4125426B2 (en) 1998-02-06 2008-07-30 三井化学ポリウレタン株式会社 Low resilience urethane foam
DE19902802A1 (en) * 1999-01-25 2000-08-03 Basf Ag Sound absorbing polyurethane
DE19924802B4 (en) * 1999-05-29 2008-02-28 Basf Ag Process for the preparation of sound-absorbing and energy-absorbing polyurethane foams
DE19924804C5 (en) * 1999-05-29 2009-02-12 Basf Se Process for the production of sound-absorbing polyurethane foams having an adhesive surface
ATE291047T1 (en) * 1999-05-31 2005-04-15 Huntsman Int Llc METHOD FOR PRODUCING LOW DENSITY FOAM AND POLYOL COMPOSITION SUITABLE THEREFOR
CN1138831C (en) * 1999-07-26 2004-02-18 亨茨曼国际有限公司 Process for preparing cold-curing flexible foams, polyol composition and reaction system for use in the process, and foams obtained thereby
AU6842500A (en) * 1999-10-07 2001-05-10 Huntsman International Llc Process for making rigid and flexible polyurethane foams containing a fire-retardant
AU7662100A (en) * 1999-11-02 2001-05-14 Huntsman International Llc Process for making high resilience foams
EP1234843A1 (en) * 2001-02-26 2002-08-28 Huntsman International Llc Process for preparing a flexible polyurethane foam
WO2002088211A1 (en) 2001-04-27 2002-11-07 Huntsman International Llc Process for making visco-elastic foam
US6994068B2 (en) * 2001-04-28 2006-02-07 Andreas Stihl Ag & Co, Kg Antivibration device
JP4856360B2 (en) * 2001-11-29 2012-01-18 ハンツマン・インターナショナル・エルエルシー Viscoelastic polyurethane
AU2003282114A1 (en) * 2002-08-02 2004-02-25 Huntsman International Llc Prepolymer, polyol composition and process for making a flexible foam
US20040073688A1 (en) * 2002-09-30 2004-04-15 Sampson Scott E. Electronic payment validation using Transaction Authorization Tokens
US6804687B2 (en) * 2002-09-30 2004-10-12 Scott E. Sampson File system management with user-definable functional attributes stored in a token action log
US8051172B2 (en) * 2002-09-30 2011-11-01 Sampson Scott E Methods for managing the exchange of communication tokens
US20060168089A1 (en) * 2002-09-30 2006-07-27 Sampson Scott E Controlling incoming communication by issuing tokens
DE10259267A1 (en) * 2002-12-17 2004-07-01 Basf Ag isocyanate adducts
US7078443B2 (en) * 2003-10-22 2006-07-18 Intellectual Property Holdings, Llc Viscoelastic foam layer and composition
US9023907B2 (en) * 2004-05-12 2015-05-05 Fritz Nauer Ag Flexible polyurethane foam
US7748184B1 (en) * 2005-02-09 2010-07-06 Intellectual Property Holdings, Llc Body panel having improved stiffness and method of making
DE102005059710A1 (en) * 2005-12-12 2007-06-14 Basf Ag Prepolymers and cellular polyisocyanate polyaddition products prepared therefrom
GB2434094A (en) * 2006-01-12 2007-07-18 Dyson Technology Ltd Drying apparatus with sound-absorbing material
EA010014B1 (en) * 2006-07-20 2008-06-30 Андрей Петрович Гончарук Process for production of stable dispersion of polymers, stable dispersion of polymers and polyurethane foam
DE102008046667A1 (en) 2008-09-10 2009-06-18 Bayer Materialscience Ag Ground cover for use as e.g. carpet in private living space for heat insulation, has layer containing viscoelastic polymer foam that exhibits hysteresis between twenty and seventy percentage during provision of compression hardness
DE102007049506B3 (en) * 2007-10-15 2009-05-28 Bayer Materialscience Ag Ground covering with viscoelastic damping properties
EP2050865B1 (en) * 2007-10-15 2014-11-26 Bayer Intellectual Property GmbH Ground cover with visco-elastic damping characteristics
EP2208744B1 (en) * 2007-11-09 2013-09-18 Mitsui Chemicals, Inc. Polyol composition, foaming composition and polyurethane foam
DE202010018631U1 (en) * 2009-12-04 2019-02-18 Mindsinsync Limited Padded absorption mat
WO2014153701A1 (en) * 2013-03-25 2014-10-02 Bayer Material Science Ag Rigid polyurethane foams with high acoustic absorption
EP2881411A1 (en) 2013-12-05 2015-06-10 Bayer MaterialScience AG Method for producing viscoelastic polyurethane foams based on phase-stable polyol formulations
US9873963B2 (en) 2014-03-17 2018-01-23 Mindsinsync Inc. Spacer mesh mat base
EP3204438B1 (en) * 2014-10-07 2019-10-02 Shell International Research Maatschappij B.V. Improvements relating to polyurethanes
JP7113011B2 (en) * 2017-06-20 2022-08-04 株式会社ブリヂストン Flexible polyurethane foam composition, flexible polyurethane foam and vehicle seat pad
DE102018130176A1 (en) * 2018-11-28 2020-05-28 Adler Pelzer Holding Gmbh Polyurethane foam formulation and sound insulation with foams based on it

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2086977A5 (en) * 1970-04-15 1971-12-31 Naphtachimie Sa
US3857800A (en) * 1970-06-19 1974-12-31 Dunlop Holdings Ltd Flexible polyurethane foams prepared from a mixture of polyether polyols
US4008189A (en) * 1974-06-03 1977-02-15 Olin Corporation Hydrophilic polyurethane foam
JPS55135128A (en) * 1979-04-10 1980-10-21 Hitachi Chem Co Ltd Production of semirigid polyurethane foam
US4469823A (en) * 1983-07-28 1984-09-04 Texaco Inc. Flexible polyurethane foams made using an aromatic polyester polyol
AU593680B2 (en) * 1986-09-05 1990-02-15 Bayer Aktiengesellschaft A process for the production of elastic, open-celled flexible polyurethane foams having increased compression hardness
US4929646A (en) * 1988-04-26 1990-05-29 The Dow Chemical Company Polyurethane foam prepared using high functionality cell openers

Also Published As

Publication number Publication date
CA1319786C (en) 1993-06-29
US5063253A (en) 1991-11-05
ES2054895T3 (en) 1994-08-16
AU3090989A (en) 1989-09-07
DE58904380D1 (en) 1993-06-24
JPH01263110A (en) 1989-10-19
JP2587290B2 (en) 1997-03-05
EP0331941A1 (en) 1989-09-13
AU624602B2 (en) 1992-06-18
DE3806476A1 (en) 1989-09-14

Similar Documents

Publication Publication Date Title
EP0331941B1 (en) Process for the preparation of cold-hardening flexible polyurethane foams having excellent deadening properties
EP0805831B1 (en) Use of toluenediamine initiated propyleneoxide polyols in rigid polyurethane foams
EP0555721A1 (en) Process for the preparation of cold-hardening flexible polyurethane foams
DE3721058A1 (en) METHOD FOR THE PRODUCTION OF COLD-CURING POLYURETHANE SOFT MOLDING FOAMS
DE3818769A1 (en) LIQUID POLYISOCYANATE MIXTURES, A METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR THE PRODUCTION OF POLYURETHANE SOFT FOAMS
DE3402310A1 (en) HARD, CLOSED-CELLED, FLAME-RESISTANT POLYURETHANE FOAMS
EP0439792B1 (en) Polyisocyanate mixtures and their use for the preparation of flexible polyurethane foams
DE19725020C2 (en) Process for the production of flexible flexible polyurethane foams
DE69506470T2 (en) Flexible polyurethane foam and process for its production
EP1650240A1 (en) Flexible polyurethane foams of low density and low hardness
EP0888393B1 (en) Process for producing hydrocarbon-blown hard polyurethane foams
EP1097953A2 (en) Process for the preparation of polyurethane foams
DE3630225A1 (en) METHOD FOR PRODUCING ELASTIC, OPEN-CELLED POLYURETHANE SOFT FOAMS WITH INCREASED TUBE HARDNESS
EP0472080B1 (en) Process for the preparation of rigid polyurethane foams
EP0731120B1 (en) Process for the preparation of highly elastic polyurethane foams
EP0422471B1 (en) Process for the preparation of flexible polyurethane foams
EP0649440B1 (en) Process for producing hard foams containing urethane groups and mainly isocyanurate groups
EP0554721B1 (en) Process for preparing soft, elastic, open-celled PUR foams
WO2001048047A1 (en) Flame-resistant hr cold-moulded foam with reduced fume density and toxicity
EP0535358B1 (en) Process for the preparation of flame-proofed rigid foams containing urethane groups
EP1237972A1 (en) Flame-resistant hr cold-moulded foam with a reduced fume density and toxicity
EP0352528A2 (en) Process for the preparation of polyurethane foams
DE3842220A1 (en) PROCESS FOR PRODUCING OPEN CELL HYDROPHILIC POLYURETHANE FOAMS
DE10000494B4 (en) Process for the preparation of soft polyurethane block or molded foams
DE4317531A1 (en) Process for the preparation of rigid polyurethane foams

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19890217

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE ES FR GB IT NL SE

17Q First examination report despatched

Effective date: 19910523

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: MILES INC.

Owner name: BAYER AG

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE ES FR GB IT NL SE

ITF It: translation for a ep patent filed
REF Corresponds to:

Ref document number: 58904380

Country of ref document: DE

Date of ref document: 19930624

ET Fr: translation filed
GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19930826

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

26 Opposition filed

Opponent name: STANKIEWICZ GMBH

Effective date: 19940218

NLR1 Nl: opposition has been filed with the epo

Opponent name: STANKIEWICZ GMBH.

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2054895

Country of ref document: ES

Kind code of ref document: T3

EAL Se: european patent in force in sweden

Ref document number: 89102703.9

PLBN Opposition rejected

Free format text: ORIGINAL CODE: 0009273

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: OPPOSITION REJECTED

27O Opposition rejected

Effective date: 19950409

NLR2 Nl: decision of opposition
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20060121

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20060123

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20060215

Year of fee payment: 18

Ref country code: GB

Payment date: 20060215

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20060228

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20070204

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20070206

Year of fee payment: 19

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20070217

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20071030

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20070417

Year of fee payment: 19

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070901

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070217

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070228

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20070219

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070219

BERE Be: lapsed

Owner name: *BAYER A.G.

Effective date: 20080228

Owner name: *MILES INC.

Effective date: 20080228

EUG Se: european patent has lapsed
NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20080901

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080901

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080218

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070217